The management of municipal solid waste (MSW) is a complex and expensive task. This is especially the case in developing countries, where waste generation rates are continuously increasing and where current MSW management strategies are focused on inadequate practices, such as landfilling and incineration, which result in numerous health and environmental problems. The anaerobic digestion (AD) of MSW has been implemented worldwide as a solution to decrease the amount of waste ending up in landfills. This process allows for the recovery of energy from the organic fraction of MSW (OFMSW) in the form of biogas, which is largely composed of methane. Therefore, the goal of the present study was to evaluate the biochemical methane potential (BMP) of the OFMSW generated within different socioeconomic strata of the Metropolitan Area of Guadalajara (MAG), Mexico. From a microscale perspective, the microbial communities within the experimental AD system were analyzed using high-throughput sequencing of the 16S rRNA gene to assess the relationship between these communities and the biogas composition. This microbial identification revealed a typical AD composition consisting of the following six phyla: Actinobacteria, Bacteroidetes, Chloroflexi, Euryarchaeota, Firmicutes, and Proteobacteria. Furthermore, through the identification of Methanobacterium and Methanosaeta, two methanogenesis pathways (hydrogenotrophic and acetoclastic) were pinpointed. From a macroscale perspective, a multi-stage Gompertz kinetic model was used to describe cumulative biogas production. This model considered the complex nature of the OFMSW substrate in order to estimate the potential level of biogas production in the MAG using a weighted average that was based on the size of the population in each socioeconomic stratum evaluated (732.8 mL⋅g−1 VS). This novel contribution to the literature provides an estimation of the potential economic, energetic, and environmental benefits of treating the OFMSW produced in the MAG through AD. Through this approach, an estimated 8.5 MWh·year−1 of electrical power could be produced, translating into 1.13 million USD of yearly revenue and resulting in reduced GHG emissions (10,519 tonne CO2eq⋅year−1).